Art of heat conversion of hydrocarbon oils



May 15, 1928. 1,670,037

F. A. HOWARD ET AL ART OF HEAT CONVERSION 0F HYDROCARBON OILS Filed Nov. 28. 1921 2 Sheets-Sheet 1 May 15, 1928. 1,670,037

F. A. HOWARD ET AL ART OF HEAT CONVERSION OF HYDROCARBON OILS Filed Nov. 2a. 1921 2 sheets-sheet 2 Patented May 15, 1928.

UNITED STATES PATENT OFFICE.

TRANI A. HOWARD AND NATHANIEL E, LOOMIS, OF ELIZABETH, NEW'JEBSEY, AB-

SIGNOBS T0 STANDARD OIL DEVELOPMENT COMPANY 0F ELIZABETH, NEW m snr, A CORPORATION or nIirLAWAzsarh Anm yois* HEAT convnnsronor nYnBocAnnoN oILs.

Application sued november as, 1921. semi no. 518,199.

The present invention relates to the heat conversion of hydrocarbon oils more particularly for the production of low boilingpoint hydrocarbon oils such as gasoline, and will be fully understood from the following description illustrated by the accompanying drawings, in which Fig. l-shows apparatus suitable for carrying out the invention, somewhat diagrammatically and partly in section, Fig. 2-shows a modifiedform of apparatus suitable for carrying out the invention, somewhat diagrammatically and partly in section.

The stock handled in practicing the present invention may suitably be any hydrocarbon oil of higher boiling-point than the desired products ofconversion. In the present process stocks of widely varying tyes may be employed, crude or residue stocks eing available as well as overhead or distillate stocks, such as the frequently employed gas-oils. Thus thefeed stock for the present process may suitably be a reduced light Mexican crude, a reduced California crude, a heavy Mexican crude or other crude or residue oil, notwithstanding the formation of extremely large amounts of carbon during the heat conversion. Thus the present process has been successfully carried out, not only on gas-oils and similar oils, but also on such oils as heavy Mexican crude petroleum having a gravity of 11.5 to 12.5 Baume and a viscosity of 800 to 900 Saybolt at 210 F.

Referring to Figure 1, the stock, which may previously have been preheated, lif desired, is fed by pump 1 through pipe 2 into a fired coil 3 mounted in a suitable furnace setting 4. This coil may be constructed, for example, of four inch pipe and may have an aggregate length, for example, of about 1,600 feet, although both dimensions may be widely varied. The coil is fired vigorously, so that the oil passing out of it has a temperature Within the range of 750 to 900 F., say 800 to 850 F. The stock is fed through the coil at a rate such that there is substantially no coke deposition in the coil, a suitable rate being 2,000 gallons er hour with a coil of the dimensions a ove described. For a given outlet temperature of the oil, the velocity of the oil in the coil may be modified in any suitable manner, for example, by increasing the firin rate and the feed rate simultaneously or by supplying steam or gas, tillaable hydrocarbon oil, such as gasoline which vaporizes at once, into the co` through the pipe 5. The added vapor oonstxtuent mixes with the oil in the coil in the form of bubbles, and increases its volume and consequently its velocity without absorbing a proportionate amount of heat in passing through the coil.

The oil passes through the coil very rapidly, acquiring an efficient cracking temperature, its passage through the coil be so fast that only incipient cracking takesullace within the coil, with relatively little or no coke formation and deposition. The oil leaving the coil does not contain a high pro portion of low boiling conversion products; the change in the oil being indicated mainly by a drop in viscosity and a small increase in Baume gravity.

After passing from the coil 3 the oil passes into the first drum 6 of a series or succession of drums or enlarged chambers. In the form of apparatus shown in the drawing, two such drums or enlar ed chambers are shown in series. These rums are of such size relative to the coil that the oil remains therein for a considerable eriod, say 11/2 to 2 hours. The first of the rums, designated by numeral 6, is lagged with a thick coating of heat insulating material so as to prevent any substantial loss of the oontained heat of the oil entering the drum. The oil, in passing through the drum 6, may drolp in temperature 50 to 75, so that the out et temperature of the oil from drum 6 is from 700 to 850. Thus where the outlet temperature of the oil from the coil is 800 to 825, the outlet temperature of the oil from the drum 6 is from 740 to 770 F. A considerable deposition of coke takes place in the drum 6 and is readily removable therefrom.

The oil passes out of the drum 6 throu h a pipe 7, the inlet of which may be at t e top of the drum or may be considerably below the top of the drum 6 as here shown. In the former case, the drum remains completely full of liquid, while lin the latter the or water or a readily vola liquid level is maintained at' the level of the outlet pipe, that is the to of the drum serves as a vapour space. The ormer arrangement is referred except in the conversion of very lig t oils such as kerosene, in which cases the latter arrangement has advantages.

The oil passing out of drum 6 to lpe 7 enters drum 8, which is an enlarge container in which the oil remains for a period approximately the same as its period of stay in drum 6. The 4drum 8 is mounted in a suitable settin so that it may be mildly heated, for exam e, by the waste combustion gases from t e settin 4 of the coil 3, which enter the setting 9 o drum 8 through Hue 10. The heat applied to the drum 8 is at no time suiiicient to raise the surface temperature of the drum above 900 F., and does not raise the temperature of the oil in the drum above its tem erature at the outlet of drum 6. In the rum 8 the temperature of the oil may be permitted to drop so that at the outlet of the drum it has a temperature of not less than about 700 F. Thus, when the temperature at the outlet of drum 6 is 740 to 770 F., the temperature at the outlet of drum 8 may suitably be 690 F. to 725 F. In each of the drums 6 and 8 there is a marked amount of conversion of the oil into the desired low boilin products. In the drum 8 there is a consi erable deposition of coke, which, by reason of the mild heating of the drum, is not baked to the surface of the latter and may be readily removed.

The products of conversion are drawn oi together from the drum 8 through the outlet pipe 11, to be cooled, for example, by heat exchange with fresh feed stock, and to be separate into Vtheir various fractions. Pressure is maintained upon the entire system at least suicient to maintain the original stock in the liquid phase at the temperature of the drums until modified by considerable pyrolysis. The pressure may, for the stock particularly described, be 150 to 180 pounds or higher. It is preferred that muc higher pressure, for example, 250 to 350 pounds be employed, particularly for converting lighter oils, such as kerosene.

In the form of ap aratus shown in Figure 2, a coil 12 of similar construction to coll 3 Figure 1 is mounted in a suitable settin in which it is highly heated so that the oil forced through it under conditions similar to those described in connection with the previous form of apparatus is brought to a temperature within t e range of 750 to 900 F., say 800 to 825 F. at the outlet from the coil. Steam or other suitable as or vapour, or va ourized`liquid may e introduced into t e coil through the pipe 13.

From the coil the heated oil passes into an enlarged chamber or drum 14, covered with a thick covering of heat insulating maving-point product takes place, the

terial, this drum being similar in character to drum 6 previously described. Here the oil is retained while a substantial conversion into low boiling-products takes place under the conditions described with the previous construction of apparatus. The eat of the oil is retained by the heavy lagging on the drum and the oil leaves the drum only slight] lowered in temperature. Thus the oil at t e outlet ot' drum 14 may have a temperature within the range of 700 to 850 F.; for example, when the oil entering the drum has a temperature of 800 to 825 F., on leaving the drum it will have a temperature of 740 to 770 F. After leaving the drum 14, the oil passes into a second heavily lagged drum 15, the construction of which is substantially similar to that of the drum 14. The oil is retained in this drum a further period during which a substantial conversion into the desired low erio being substantially the same as that uring which the oil remains in the drum 14. 1n order that the oil may not fall below an eiiicient cracking temperature of say 680 t0 7 00 F in the drum l5, means are provided for supplying heat internally within the drum. This heat is suitably supplied by introducing into the drum in suitably regulated quantities a forni of oxygen containing gas, such as air. At the temperatures prevailing within the drum, the supply of oxygen causes immediate and spontaneous combustion of corresponding quantities of the hydrocarbon material within the drum, the heat thus liberated maintaining the oil at the proper temperature.

In the form of apparatus illustrated, the air or other oxygen containing gas is forced by pump 16 through a suitable heating device 17, in which it is brought to a temperature of preferably T00 to 900 F. From the heating device 17 the heated air passes through valved pipe 18 into a distributing head 19 within the drum. The pl'eheating of the air makes the heat supplied b com bustion Within the drum substantially entirely available for heating and maintaim ing the tem erature of the oil.

The supp y of air or oxygen containing gas is regulated by the valved pipe 18 to supply sufficient heat within the drum so that the temperature of the products of conversion leaving the drum through outlet pi 20 will be not less than 700 to 750 F. Tlig supply of air should in general, however, not be so great as to bring the temperature of the oil leaving the drum 15 above that of the oil leaving the coil 12. It is usually sufficient that oil leaving the drum shall be above 680 to 7 00 F. and not more than 50 to below the tem erature of the oil leaving the drum 14. or example, when the oil leaving the drum 14 has a temperature llU . ing the waste combustion of 740 to 770 F. the temperature of the roducts leaving the drum 15 may be from 25 t0 750 F.

In the case of the 12 Baum oil referred to the rocess as described in connection with eit 1er form of apparatus effects such conversion of the oil t at when distilled it will roduce about 20 to 25% or upwards of distillate having a gravity of asoline or kerosene, say for exam le, 48 aum, and the rate of feed and withdrawal of oil may be adjusted to produce approximately this conversion.

We claim:

1. In apparatus for the conversion of oil, the combination of a. coil means for forcing oil therethrough, means or a plying highly heated combustion gases to tlie coil, an enlarged unheated chamber into which the coil discharges, said chamber being provided with means for hindering the escape of heat and having a. single outlet, a second enlarged chamber into which the first mentioned chamber discharges, and means for supplygases to heat the second chamber after having been applied to the coil.

2. In apparatus for the conversion of oil, a combination of a coil, means for forcing oil therethrou h, means for heating the coil to secure crac ing temperature therein, an enlarged chamber into which the coil discharges, said chamber being provided with means for hinderin the escape of heat from the chamber, there y maintainin a cracking temperature therein a secon( enlarged chamber into which t e first mentioned chamber discharges, and means for supplying heat internally within the second chamber to maintain a cracking temperature therein.

3. In apparatus for the conversion of oil, a combination of a coil, means for forcing oil therethrough, means for highly heating the coil to secure cracking temperature therein, an enlarged chamber into which the coil discharges, means for retaining the heat of the oil within said chamber to maintain a crackin temperature therein, a second enlarged c amber into which the heated oil from the first mentioned chamber is discharged, and means for supplying free oxygen containing gas into the second chamber, thereby maintaining a cracking temperature therein.

4. In apparatus for the conversion of oil, a combination of a coil, means for forcing oil therethrough, means for highly heating the coil to secure a cracking tem erature therein, an enlarged chamber into w ich the coil discharges, said chamber having a single outlet means for retaining the heat of the oil within said chamber, to maintain a cracking temperature therein, a second en larged chamber into which the heated oil from the rst mentioned chamber is dischargred through said outlet, means for heating ee oxygen containing gas, and means for supplyin the heated o gen containing gas within t e second cham r to maintain a cracking temperature therein.

5. In apparatus for heating oil, an externally unheated chamber, means for continually sup lying heated oil within said chamber, an for maintaining a li uid body of such oil therein, such chamber aving a. single outlet, means for suppl in an oxygen containing gas within the e am r whereby combustion of correspondin proportions of the oil product contained t erein is caused to maintain the temperature of the oil body, and means for continually withdrawin the heated conversion products from said c iamber through said slngle outlet.

6. The process of converting hydrocarbon oils into h drocarbon oils of lower boilingpoint which comprises forcing the oil to be converted throu h a highly heated confined passage-way wit a velocity suiiicient to prevent substantial deposition of coke, the oil being thereby brought to conversion temperature, discharging the oil into an enlarged chamber while confining therein the contained heat of the oil, to maintain the oil at conversion temperature and passing the combined products of conversion together from said enlarged chamber into a second enlarged chamber, the walls of which are heated to maintain conversion temperature of the oil, the wall temperature thereof being not above 900 F. i

7. The process of convertin hydrocarbon oils into h drocarbon oils of Iower boilingpoint whic comprises forcing the oil to be converted through a highly heated confined passage-way with sufficient velocity to prevent substantial deposition of coke the oi] being thereby brought to conversion temperature, discharging the oil into and through a succession of enlarged chambers, the contained heat of the oil being confined in the earlier of said chambers to maintain the oil therein at conversion temperature and the later of said chambers being heated only sufficiently to maintain the oil at conversion temperature.

8. The process of converting hydrocarbon oils into hydrocarbon oils of lower boilingpoint which comprises forcing the oil through a confined assage, heating the passage so that the oil ischarged therefrom has a temperature of 750 to 900 F., the velocity of the oil in the confined passa e being suc that no substantial amount o coke is deposited therein, discharging the oil into an enlarged chamber While confining therein the contained heat of the oil to maintain it at a conversion temperature and passing the products from said enlarged chamber, into a second enlarged chamber supplying heat EIS llo

IRI

to said second chamber suicient to maintain the oil at conversion temperature and not more than sufficient to maintain the temperature of the oil at its entrance temperature.

9. The process of converting hydrocarbon oils into hydrocarbon oils of ower bolhngpoint which com rises forcln the o1! through a confine passage, app ying heat to bring the oil to a temperature of 800 to 825 F. when discharged from the passa e, the oil being forced therethrough with su cient velocity to revent substantial deposition of coke, disc arging the oil into an enlarged chamber while confining therein the contained -heat of the oil to maintain it at conversion temperature, discharging the oil from said chamber at a temperature of 740 to 770 F. into a second enlarged chamber, and heating said second chamber so that the oil discharged therefrom has a temperature of 675 to 725 F.

10. The process of converting hydrocarbon oils into hydrocarbon oils of lower boiling-point which .comprises forcing the oil through a confined assage, heating the passage so that the oil ischarged therefrom has a temperature of 750 to 900 F., the velocit?Y of the oil in the confined passage being suc i that no substantial amount of coke is deposited there, discharging the oil into an enlarged chamber while confining therein the contained heat of the oil, and assing the product from said enlarged cham r into a second enlarged chamber, introducing an oxygen containing gas into the second enlarged chamber whereby spontaneous combastion of corresponding proportions of the products therein is caused and regulating the quantity of such gas supplied to maintain the temperature of the oil in the second enlarged chamber notbelow 680 to 700 F.

11. The process of converting hydrocarbon oils into hydrocarbon oils of lower boiling-point which comprises forcing the oil through a highly heated confined passa e with a velocity sufficient to prevent a sufistantial deposition of coke whereby the oil is brought to a cracking temperature, discharging the oil into an enlarged chamber while confining therein the contained heat of the oil to maintain it at cracking temperature, passing the products from such enlarged chamber into a second enlarged chamber, the heat supplied to `the oil being such that it enters the second enlarged chamber at a temperature not below 680 to 700 F., and supplying within the second chamber regulated quantities of free oxygen containing gas to substantially maintain said temperature.

12. The process of convertingr hydrocarbon oils into hydrocarbon oils of lower boiling-point which comprises forcin the oil through a highly heated confine passage Lemos? with a velocity sufficient to reventa substantial deposition of coke, lschargm the oil into an enlarged chamber while con ing therein the contained heat of the oil, assmg the products from such enlarged c amber into a second enlarged chamber, the heat supplied to the oil being such that 1t enters the second enlarged chamber at a temperature not below 680 to 700 F., and supplying within the second chamber regulated quantities of heated free oxygen containinggas. 0

13. The process of heat treating oils to effect conversion thereof, introducing heated oil products at a temperature of 700 to 850 F., 1nto a chamber, supplying air within said chamber, maintaining a liiiid body of said oil products therein, where y combustion of corresponding proportions of said oil products is s ontaneously effected and heat supplied within said chamber, and removin the conversion products from within sai chamber, the air supplied being regulated to maintain the temperature of the products removed from said chamber not below 680 to 700 F.

14. The process of heat treating hydrocarbon oils to effect conversion thereof, supplying oil products at a temperature of 740 to 770 F. Within a chamber, maintaining a body of the oil products therein, introducing air into said chamber whereby spontaneous combustion of corresponding proportions of the oil products therein is effected and heat is supplied therein, and withdrawing the conversion products from said chamber, the supply of air being regulated so that the temperature of the products withdrawn from said chamber is from 690 to 720 F. and maintaining pressure within said chamber sufficient to retain some of said products in liquid state.

15. The process of heat treating hydrocarbon oils to effect conversion thereof, supplying oil products at a temperature of 740 to 770 F. within a chamber, introducing heated air into such chamber whereby spontaneous combustion of corresponding proportions of the oil products therein is effected and heat is supplied therein, and withdrawing the conversion products from said chamber, the supply of heated air being regulated so that the temperature of the products withdrawn from said chamber is from 690 to 720 F.

16. The method of heat treating oils for effecting conversion thereof which comprises rapidly heating such oils, maintaining a liquid body of the heated oil at a temperature not below 680 F., and introducing free oxygen containing gus into the heated oil in proportion to cause sufficient combustion to maintain the temperature of the oil at not below 680 F.

17. The process of heat treating oils to effect conversion thereof, introducing heated oil products at a temperature of at least 700 F., into a chamber, supplying air within said chamber, maintaining a liquid body of said oil products therein, whereby combustion of corresponding proportions of said oil products is spontaneously effected and heat supplied within said chamber, and removing the conversion products from within said chamber, the air supplied being regulated to maintain the temperature of the products removed from said chamber not below 700 F.

18. The process of converting hydrocarbon oils into hydrocarbon oils of lower boiling point which comprises forcing the oil to be converted through a highly heated confined passageway to bring the oil to conversion temperature and with a velocity sulicient to prevent substantial deposition of coke, maintaining the oil at conversion tem- Y"said enlarged chamber t roug a single outlet therefrom.

FRANK A. HOWARD. NATHANIEL E. LOOMIS.

DISCLAIMER t 1,670,037 .-Franlc A. Howard and Nathaniel E. Loomis, Elizabeth, N. J. An'rior HEAT CONVERSION oF HYDnocARBoN OILS.

Patent dated May 15, 1928.

Disclaimer filed November 6, 1931, by the assignee, Standard Oil Development Company. Hereby'enters this disclaimer:

To the process described and set forth in claim 7, except when, in the conduct of the said process, the contained .heat of the oil is confined in the earlier of the enlarged chambers by insulation or lagging and without the rapplication of heated gases externally thereto.

To the process described and set forth in claim 8, except when in the conduct of the said process, the contained heat of the oil lsconfined 1n the f irst enla ed chamber by applying insulation or lagging thereto and Without the application of eated gases thereto. i

[Oficial Gazette December 1, 1931.]

effect conversion thereof, introducing heated oil products at a temperature of at least 700 F., into a chamber, supplying air within said chamber, maintaining a liquid body of said oil products therein, whereby combustion of corresponding proportions of said oil products is spontaneously effected and heat supplied within said chamber, and removing the conversion products from within said chamber, the air supplied being regulated to maintain the temperature of the products removed from said chamber not below 700 F.

18. The process of converting hydrocarbon oils into hydrocarbon oils of lower boiling point which comprises forcing the oil to be converted through a highly heated confined passageway to bring the oil to conversion temperature and with a velocity sulicient to prevent substantial deposition of coke, maintaining the oil at conversion temperature to secure conversion thereof, discharging products of such conversion into a. chamber while at conversion temperature and supplying within said chamber an oxygen-containing gas to maintain the products therein at conversion temperature.

19. The process of converting hydrocarbon oils which comprises continuously assing the oil to be converted through a highly heated confined passageway to bring the oil to conversion temperature, continuously passing the oil at conversion temperature into an enlarged chamber, supplying within said chamber an oxygen containing gas to maintain conversion temperature therein, and continuously takin olf roducts from Y"said enlarged chamber t roug a single outlet therefrom.

FRANK A. HOWARD. NATHANIEL E. LOOMIS.

DISCLAIMER t 1,670,037 .-Franlc A. Howard and Nathaniel E. Loomis, Elizabeth, N. J. An'rior HEAT CONVERSION oF HYDnocARBoN OILS.

Patent dated May 15, 1928.

Disclaimer filed November 6, 1931, by the assignee, Standard Oil Development Company. Hereby'enters this disclaimer:

To the process described and set forth in claim 7, except when, in the conduct of the said process, the contained .heat of the oil is confined in the earlier of the enlarged chambers by insulation or lagging and without the rapplication of heated gases externally thereto.

To the process described and set forth in claim 8, except when in the conduct of the said process, the contained heat of the oil lsconfined 1n the f irst enla ed chamber by applying insulation or lagging thereto and Without the application of eated gases thereto. i

[Oficial Gazette December 1, 1931.] 

